Khadiwale notched up his highest score in first-class cricket as he converted his overnight century into a monumental 262 to power Maharashtra to 635 all out in their first innings at the Subrata Roy Sahara Stadium.
Khadiwale faced 396 balls during his stay at the crease and hit an astonishing 32 fours and two sixes.
The hosts added 274 runs to their overnight total of 361 for three before being bowled out at the stroke of tea.
The day also belonged to Goa's off-spinner Amit Yadav, who picked up seven wickets for 155 runs from his 45.4 overs.
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Goa finished the day at 73 for one, losing opener Amogh Desai to Mundhe for 28.
Swapnil Asnodkar (25 batting) and Hanumant Gadekar (11) were at the crease.
Brief Scores: Maharashtra 635 all out in 153.4 overs (Harshad Khadiwale 262, Kedhar Jadhav 106, Srikanth Mundhe 75; Amit Yadav 7/155).
Goa: 73 for 1 in 26 overs (Swapnil Asnodkar 25 batting; Srikanth Mundhe 1/23).